CN102623189B - Method for preparing electrode material for graphene/manganese dioxide thin-film asymmetrical supercapacitor - Google Patents
Method for preparing electrode material for graphene/manganese dioxide thin-film asymmetrical supercapacitor Download PDFInfo
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Abstract
The invention relates to a method for preparing an electrode material for a graphene/manganese dioxide thin-film asymmetrical supercapacitor, which comprises the following steps of: (1) dispersing graphite oxides into ultrapure water, then sequentially carrying out ultrasonic processing and centrifugation on the obtained mixture, taking supernatant fluid, adding hydrazine hydrates and ammonia water as a reducing agent into the supernatant fluid, then stirring the obtained object, and carrying out heat preservation on the stirred mixture for 1-2 hours at the temperature of 90-100 DEG C so as to obtain graphene powder; (2) dispersing manganese salts into an isopropyl alcohol solution, carrying out ultrasonic processing on the obtained object, and then carrying out reflux condensation on the obtained object at the temperature of 80-85 DEG C so as to obtain manganese dioxide powder; and (3) dispersing the graphene powder into ultrapure water so as to prepare a graphene dispersion, dispersing the manganese dioxide powder into ultrapure water so as to obtain a manganese dioxide dispersion, and finally, sequentially carrying out stratified suction filtration on the graphene dispersion and the manganese dioxide dispersion so as to obtain the electrode material. The method disclosed by the invention is simple in preparation process, and a prepared electrode material for a supercapacitor is good in chemical stability and high in specific capacitance and has a flexible structure, therefore, the method has broad application prospects.
Description
Technical field
The invention belongs to the preparation field of super capacitor material, particularly a kind of preparation method of Graphene/manganese dioxide membrane Asymmetric Supercapacitor electrode material.
Background technology
Manganese dioxide resource is extensive, cheap, environment friendliness, and excellent conductivity is widely used as battery electrode material and oxidation catalyst material.Electrode material as ultracapacitor just grows up in recent years, it shows good capacitance characteristic in neutral electrolyte, maximum theory reaches 1370F/g than electric capacity, and potential window is wider, in water system electrolyte, can reach 1V voltage, become the study hotspot of recent electrode material for super capacitor.
Graphene be can by graphite oxide reduce and a kind of new material.Since the research group of the Novoselov of University of Manchester in 2004 and Geim finds Graphene, Graphene becomes rapidly the hot issue of physics, chemistry and materialogy, has started the research boom of researcher to its character and application.With regard to conductivity, Graphene is zero gap semiconductor, its stable lattice structure makes carbon atom have excellent conductivity, wherein the movement velocity of electronics has reached 1/300 of the light velocity, far having exceeded the movement velocity of electronics in general conductor, is the current known outstanding material of electric conductivity.Meanwhile, Graphene has 2630m
2the theoretical specific area of/g and unique charge carrier characteristic, this provides theoretical foundation for it becomes good electrode material for super capacitor.Manganese dioxide and Graphene compound, manganese dioxide can hinder the compound of graphene film interlayer on the one hand, is conducive to Graphene and disperses, and Graphene can promote the electric transmission on manganese dioxide surface on the other hand, thereby improve manganese dioxide utilance, performance cooperative effect.The people such as Z.S.Wu have reported a kind of method of having prepared manganese dioxide nano line/Graphene and Graphene high-performance Asymmetric Supercapacitor at ACS Nano 4 (2010) 5835-5842, its energy density has reached 30.4Wh/kg, has good power density and cyclical stability simultaneously.The people such as Q.Cheng have reported the manganese dioxide/graphene composite material of a kind of electrochemical deposition for the preparation of ultracapacitor at Carbon49 (2011) 2917-2925, this material has reached the ratio electric capacity of 328F/g, has the energy density of 11.4Wh/kg and the power density of 25.8kW/kg simultaneously.
But above prepared manganese dioxide/graphene composite material is all pulverulence, to prepare ultracapacitor and need to add 15～40% conductive agent and binding agent, this has increased quality and the cost of ultracapacitor greatly.
Have not yet to see the report of Graphene/manganese dioxide membrane Asymmetric Supercapacitor electrode material.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of Graphene/manganese dioxide membrane Asymmetric Supercapacitor electrode material, the method technique is simple, be easy to suitability for industrialized production, prepared Graphene/manganese dioxide membrane Asymmetric Supercapacitor electrode material is higher than electric capacity, conduct electricity very well, film forming procedure is simple, without conductive agent binding agent.
The preparation method of a kind of Graphene/manganese dioxide membrane Asymmetric Supercapacitor electrode material of the present invention, comprising:
(1) preparation of graphene powder:
At room temperature, graphite oxide is distributed in ultra-pure water, obtain the suspension of graphite oxide, the ultrasonic rear centrifugal unpeeled graphite that removes, get supernatant and add hydrazine hydrate and ammoniacal liquor as reducing agent, then stir, then in 90～100 ℃ of insulation 1～2h, after filtering and washing, freeze drying, grind, obtain graphene powder;
(2) preparation of manganese dioxide powder:
Manganese salt is dispersed in aqueous isopropanol, obtains the isopropanol suspension of manganese salt, ultrasonic after in 80-85 ℃ of condensing reflux, centrifuge washing, grind after dry, obtain manganese dioxide powder;
(3) graphene powder of being prepared by step (1) is distributed in ultra-pure water, is mixed with the graphene dispersing solution of 0.2～0.5mg/mL, ultrasonic; Manganese dioxide powder prepared by step (2) is distributed in ultra-pure water, obtains manganese dioxide dispersion liquid, and in described manganese dioxide dispersion liquid, the concentration of manganese dioxide is identical with the concentration of Graphene in graphene dispersing solution; Finally, by above-mentioned graphene dispersing solution and manganese dioxide dispersion liquid layering suction filtration successively, obtain Graphene/manganese dioxide layered film of stratiform.
In the suspension of the graphite oxide described in step (1), the concentration of graphite oxide is 0.25～1mg/mL.
The ultrasonic time described in step (1) is 1～2h.
Centrifugal process described in step (1) is: rotating speed is 2000～3500r/min, and centrifugation time is 15～40min.
The mass ratio of the hydrazine hydrate described in step (1) and graphite oxide is 1: 1～5: 1, and the mass ratio of ammoniacal liquor and graphite oxide is 10: 1～20: 1.
The time of stirring described in step (1) is 10～60min, and filtering and washing process is ultra-pure water filtering and washing 6～10 times.
Manganese salt described in step (2) is manganese chloride, manganese sulfate or manganese carbonate, preferential manganese chloride.
In the isopropanol suspension of the manganese salt described in step (2), the concentration of manganese salt is 0.03～0.01mmol/mL.
The ultrasonic time described in step (2) is 15～40min, and the time of condensing reflux is 10～40min.
Centrifuge washing process described in step (2) is: rotating speed is 7000～8500r/min, and centrifugation time is 5～15min, absolute ethanol washing 3～6 times, ultra-pure water washing 3～6 times.
The ultrasonic time described in step (3) is 0.5～2h.
The volume ratio of the layering suction filtration Graphite During The Process alkene dispersion liquid described in step (3) and manganese dioxide dispersion liquid is 1: 2～2: 1.
Graphene/manganese dioxide membrane Asymmetric Supercapacitor electrode material suction filtration method direct formation of film at surface prepared by this method, without conductive agent and binding agent, retain energy density and the power density of this height of material simultaneously, there is boundless application prospect in flexible electronic energy storage device field.
Beneficial effect
1, preparation technology of the present invention is simple, and film forming procedure, without conductive agent, binding agent, is suitable for suitability for industrialized production;
2, Graphene/manganese dioxide membrane Asymmetric Supercapacitor electrode material voltage form wide ranges that prepared by the present invention, energy density and power density are high, conduct electricity very well;
3, Graphene/manganese dioxide membrane Asymmetric Supercapacitor electrode material that the present invention obtains has higher flexibility, is expected to be applied to the fields such as electric automobile, communication, flexible electronic product and signal controlling.
Accompanying drawing explanation
Fig. 1 is the Graphene prepared of embodiment 1 and the X ray diffracting spectrum of manganese dioxide powder;
Fig. 2 is the field transmitting Electronic Speculum picture of Graphene/manganese dioxide membrane of preparing of embodiment 1;
Fig. 3 is the impedance spectrum under Graphene/manganese dioxide membrane Asymmetric Supercapacitor electrode material two electrode conditions of preparing of embodiment 1, and illustration is the enlarged drawing that approaches starting point region;
To be that Graphene/manganese dioxide membrane Asymmetric Supercapacitor electrode material of preparing of embodiment 1 is different under two electrode conditions in 1M sodium sulphate electrolyte sweep fast cyclic voltammetry curve figure to Fig. 4;
Fig. 5 is the curve chart of constant current charge-discharge first of Graphene/manganese dioxide membrane Asymmetric Supercapacitor electrode material different current densities in 1M sodium sulphate electrolyte of preparing of embodiment 1.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
Take 0.05g graphite oxide and be distributed to ultrasonic dispersion 1h in 100mL ultra-pure water, the centrifugal 30min of 3000r/min removes unpeeled graphite oxide, supernatant is removed, added 0.05g hydrazine hydrate and 1g ammoniacal liquor, magnetic agitation 15min, then the beaker that solution is housed is placed in oil bath pan, 95 ℃ of insulation 1h, obtain black dispersion liquid, ultra-pure water filtering and washing 6 times, after freeze drying, grind, obtain graphene powder.Taking 0.27g tetrahydrate manganese chloride is distributed in 50mL isopropyl alcohol, ultrasonic dispersion 30min, join in there-necked flask, 83 ℃ of oil baths under mechanical agitation, condensing reflux 30min, takes out the brown color dispersion liquid obtaining, and centrifugal rotational speed is to be that under 10min condition, ethanol washs 4 times the 7000r/min time, ultra-pure water washing 4 times, dry rear grinding obtains manganese dioxide powder.The graphene powder of preparation is distributed in ultra-pure water, be mixed with the dispersion liquid of 0.2mg/mL, ultrasonic dispersion 0.5h, the manganese dioxide powder of preparation is distributed in ultra-pure water simultaneously, be mixed with the dispersion liquid of 0.2mg/mL, above-mentioned graphene dispersing solution and manganese dioxide dispersion liquid are pressed to 1: 1 volume ratio layering suction filtration successively, obtain Graphene/manganese dioxide layered film of stratiform.
Fig. 1 is the Graphene of preparation and the X ray diffracting spectrum of manganese dioxide powder, the diffraction maximum of manganese dioxide is mated with standard P DF card 44-0141, there is no other obviously assorted peaks, show that the manganese dioxide of preparing is purer, good crystallinity, in Graphene, do not occur that the peak of graphite oxide illustrates that it is reduced into Graphene.
Fig. 2 is the field transmitting Electronic Speculum picture of Graphene/manganese dioxide layered film, can find out that bar-shaped manganese dioxide is gathered into felted and upper and lower two Graphene films form sandwich structure, and the thickness of laminated film is 2 microns of left and right.
Fig. 3 is using Graphene/manganese dioxide layered film as positive pole, and graphene film is as negative pole, and the impedance spectrum of composition super capacitor two electrode tests, can be analyzed and be shown that the electric charge transmission resistance of product is lower by the enlarged drawing that approaches initial point region.
Fig. 4 is using Graphene/manganese dioxide layered film as positive pole, graphene film is as negative pole, composition super capacitor two electrode test differences are swept fast feature cyclic voltammetry curve figure, can find out and under high sweep speed, still can keep good rectangle at 2V/s, show that as calculated this structure has reached the energy density of 34.3Wh/kg and the power density of 16.5kW/kg.
Fig. 5 is the curve chart of constant current charge-discharge first that product and graphene film form different current densities in super capacitor two electrode tests, shows that product has good charge-discharge performance.
Embodiment 2
Take 0.05g graphite oxide and be distributed to ultrasonic dispersion 1h in 50mL ultra-pure water, the centrifugal 40min of 2000r/min removes unpeeled graphite oxide, supernatant is removed, added 0.1g hydrazine hydrate and 0.7g ammoniacal liquor, magnetic agitation 10min, then the beaker that solution is housed is placed in oil bath pan, 100 ℃ of insulation 1h, obtain black dispersion liquid, ultra-pure water filtering and washing 10 times, after freeze drying, grind, obtain graphene powder.Taking 0.17g manganese sulfate monohydrate is distributed in 100mL isopropyl alcohol, ultrasonic dispersion 15min, join in there-necked flask, 83 ℃ of oil baths under mechanical agitation, condensing reflux 10min, takes out the brown color dispersion liquid obtaining, and centrifugal rotational speed is to be that under 5min condition, ethanol washs 3 times the 8500r/min time, ultra-pure water washing 6 times, dry rear grinding obtains manganese dioxide powder.The graphene powder of preparation is distributed in ultra-pure water, be mixed with the dispersion liquid of 0.5mg/mL, ultrasonic dispersion 2h, the manganese dioxide powder of preparation is distributed in ultra-pure water simultaneously, be mixed with the dispersion liquid of 0.5mg/mL, above-mentioned graphene dispersing solution and manganese dioxide dispersion liquid are pressed to 1: 2 volume ratio layering suction filtration successively, obtain Graphene/manganese dioxide layered film of stratiform.
X-ray diffraction analysis is indicated as the thing phase of manganese dioxide and Graphene, Electronic Speculum picture has shown to obtain the layered composite structure of manganese dioxide and Graphene, the impedance spectrum analysis of product and graphene film composition super capacitor two electrode tests shows that the structure charge transmission resistance obtaining is lower, cyclic voltammetry curve assay products and Graphene composition there is higher ratio capacitive property, constant current charge-discharge analysis has good charge-discharge performance.
Take 0.025g graphite oxide and be distributed to ultrasonic dispersion 2h in 100mL ultra-pure water, the centrifugal 15min of 3500r/min removes unpeeled graphite oxide, supernatant is removed, added 0.125g hydrazine hydrate and 0.25g ammoniacal liquor, magnetic agitation 60min, then the beaker that solution is housed is placed in oil bath pan, 90 ℃ of insulation 2h, obtain black dispersion liquid, ultra-pure water filtering and washing 8 times, after freeze drying, grind, obtain graphene powder.Taking 0.17g manganese carbonate is distributed in 50mL isopropyl alcohol, ultrasonic dispersion 40min, join in there-necked flask, 83 ℃ of oil baths under mechanical agitation, condensing reflux 40min, takes out the brown color dispersion liquid obtaining, and centrifugal rotational speed is to be that under 15min condition, ethanol washs 6 times the 7000r/min time, ultra-pure water washing 3 times, dry rear grinding obtains manganese dioxide powder.The graphene powder of preparation is distributed in ultra-pure water, be mixed with the dispersion liquid of 0.3mg/mL, ultrasonic dispersion 1h, the manganese dioxide powder of preparation is distributed in ultra-pure water simultaneously, be mixed with the dispersion liquid of 0.3mg/mL, above-mentioned graphene dispersing solution and manganese dioxide dispersion liquid are pressed to 2: 1 volume ratios layering suction filtration successively, obtain Graphene/manganese dioxide layered film of stratiform.
X-ray diffraction analysis is indicated as the thing phase of manganese dioxide and Graphene, Electronic Speculum picture has shown to obtain the layered composite structure of manganese dioxide and Graphene, the impedance spectrum analysis of product and graphene film composition super capacitor two electrode tests shows that the structure charge transmission resistance obtaining is lower, cyclic voltammetry curve assay products and Graphene composition there is higher ratio capacitive property, constant current charge-discharge analysis has good charge-discharge performance.
Embodiment 4
Take 0.05g graphite oxide and be distributed to ultrasonic dispersion 1.5h in 80mL ultra-pure water, the centrifugal 25min of 3000r/min removes unpeeled graphite oxide, supernatant is removed, added 0.15g hydrazine hydrate and 0.7g ammoniacal liquor, magnetic agitation 40min, then the beaker that solution is housed is placed in oil bath pan, 95 ℃ of insulation 1h, obtain black dispersion liquid, ultra-pure water filtering and washing 9 times, after freeze drying, grind, obtain graphene powder.Taking 0.2g tetrahydrate manganese chloride is distributed in 50mL isopropyl alcohol, ultrasonic dispersion 30min, join in there-necked flask, 83 ℃ of oil baths under mechanical agitation, condensing reflux 20min, takes out the brown color dispersion liquid obtaining, and centrifugal rotational speed is to be that under 15min condition, ethanol washs 5 times the 8000r/min time, ultra-pure water washing 4 times, dry rear grinding obtains manganese dioxide powder.The graphene powder of preparation is distributed in ultra-pure water, be mixed with the dispersion liquid of 0.2mg/mL, ultrasonic dispersion 1h, the manganese dioxide powder of preparation is distributed in ultra-pure water simultaneously, be mixed with the dispersion liquid of 0.2mg/mL, above-mentioned graphene dispersing solution and manganese dioxide dispersion liquid are pressed to 1: 1 volume ratio layering suction filtration successively, obtain Graphene/manganese dioxide layered film of stratiform.
X-ray diffraction analysis is indicated as the thing phase of manganese dioxide and Graphene, Electronic Speculum picture has shown to obtain the layered composite structure of manganese dioxide and Graphene, the impedance spectrum analysis of product and graphene film composition super capacitor two electrode tests shows that the structure charge transmission resistance obtaining is lower, cyclic voltammetry curve assay products and Graphene composition there is higher ratio capacitive property, constant current charge-discharge analysis has good charge-discharge performance.
Claims (6)
1. a preparation method for Graphene/manganese dioxide membrane Asymmetric Supercapacitor electrode material, comprising:
(1) at room temperature, graphite oxide is distributed in ultra-pure water, obtain the suspension of graphite oxide, the ultrasonic rear centrifugal unpeeled graphite that removes, get supernatant and add hydrazine hydrate and ammoniacal liquor as reducing agent, then stir, then in 90～100 ℃ of insulation 1～2h, after filtering and washing, freeze drying, grind, obtain graphene powder; Wherein, the described ultrasonic time is 1～2h; Described centrifugal process is: rotating speed is 2000～3500r/min, and centrifugation time is 15～40min; The time of described stirring is 10～60min, and filtering and washing process is ultra-pure water filtering and washing 6～10 times; The mass ratio of hydrazine hydrate and graphite oxide is 1:1～5:1, and the mass ratio of ammoniacal liquor and graphite oxide is 10:1～20:1;
(2) manganese salt is dispersed in aqueous isopropanol, obtains the isopropanol suspension of manganese salt, ultrasonic after in 80-85 ℃ of condensing reflux, centrifuge washing, grind after dry, obtain manganese dioxide powder; Wherein, in the isopropanol suspension of manganese salt, the concentration of manganese salt is 0.03～0.01mmol/mL;
(3) graphene powder of being prepared by step (1) is distributed in ultra-pure water, is mixed with the graphene dispersing solution of 0.2～0.5mg/mL, ultrasonic; Manganese dioxide powder prepared by step (2) is distributed in ultra-pure water, obtains manganese dioxide dispersion liquid, and in described manganese dioxide dispersion liquid, the concentration of manganese dioxide is identical with the concentration of Graphene in graphene dispersing solution; Finally, by above-mentioned graphene dispersing solution and manganese dioxide dispersion liquid layering suction filtration successively, to obtain final product.
2. the preparation method of a kind of Graphene/manganese dioxide membrane Asymmetric Supercapacitor electrode material according to claim 1, is characterized in that: in the suspension of the graphite oxide described in step (1), the concentration of graphite oxide is 0.25～1mg/mL.
3. the preparation method of a kind of Graphene/manganese dioxide membrane Asymmetric Supercapacitor electrode material according to claim 1, is characterized in that the manganese salt described in step (2) is manganese chloride, manganese sulfate or manganese carbonate.
4. the preparation method of a kind of Graphene/manganese dioxide membrane Asymmetric Supercapacitor electrode material according to claim 1, is characterized in that: the ultrasonic time described in step (2) is 15～40min, and the time of condensing reflux is 10～40min; Described centrifuge washing process is: rotating speed is 7000～8500r/min, and centrifugation time is 5～15min, absolute ethanol washing 3～6 times, ultra-pure water washing 3～6 times.
5. the preparation method of a kind of Graphene/manganese dioxide membrane Asymmetric Supercapacitor electrode material according to claim 1, is characterized in that: the ultrasonic time described in step (3) is 0.5～2h.
6. the preparation method of a kind of Graphene/manganese dioxide membrane Asymmetric Supercapacitor electrode material according to claim 1, is characterized in that: the volume ratio of the layering suction filtration Graphite During The Process alkene dispersion liquid described in step (3) and manganese dioxide dispersion liquid is 1:2～2:1.
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| CN103474251B (en) * | 2013-08-13 | 2016-08-10 | 常州大学 | A kind of asymmetric electrochemical capacitor of organic electrolyte system and preparation method thereof |
| CN103588198B (en) * | 2013-11-20 | 2015-09-30 | 上海应用技术学院 | A kind of preparation method of graphene/manganese dioxide composite material |
| CN104810504B (en) * | 2014-01-24 | 2017-12-19 | 中国科学院金属研究所 | A kind of Flexible graphene collector and active material integrated electrode pole piece and preparation method thereof |
| CN105428093A (en) * | 2015-12-31 | 2016-03-23 | 厦门大学 | Preparation method of paper type super capacitor electrode |
| WO2018032324A1 (en) * | 2016-08-16 | 2018-02-22 | 肖丽芳 | Method for manufacturing manganese dioxide-graphene foam composite electrode |
| CN107275112B (en) * | 2017-08-15 | 2018-10-16 | 中国工程物理研究院激光聚变研究中心 | Irradiation method prepares MnO2The method for adulterating bamboo charcoal based super capacitor electrode material |
| CN108258334B (en) * | 2018-01-19 | 2020-11-24 | 北京大学深圳研究生院 | Composite flexible electrode, preparation method and application thereof |
| CN111341568A (en) * | 2020-03-17 | 2020-06-26 | 浙江浙能技术研究院有限公司 | Preparation method of graphene mixed film |
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